CN112499590A - Process and apparatus for producing anhydrous hydrogen fluoride - Google Patents

Process and apparatus for producing anhydrous hydrogen fluoride Download PDF

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Publication number
CN112499590A
CN112499590A CN202011344281.4A CN202011344281A CN112499590A CN 112499590 A CN112499590 A CN 112499590A CN 202011344281 A CN202011344281 A CN 202011344281A CN 112499590 A CN112499590 A CN 112499590A
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tower
stage
hydrogen fluoride
continuous extraction
anhydrous hydrogen
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CN112499590B (en
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李明
黄相振
李冠华
张立维
何广昌
范志东
孙曙光
黄琼
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China Nuclear Power Engineering Co Ltd
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China Nuclear Power Engineering Co Ltd
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    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
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Abstract

The invention discloses a process and a device for producing anhydrous hydrogen fluoride, wherein the process comprises the following steps: 1) extracting agent straight-chain primary alcohol CnH2n+2OH、H2Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extraction phase at the top of the continuous extraction tower, n is more than or equal to 8 and less than or equal to 10, and n is an integer; 2) introducing the extract phase into a first-stage rectifying tower for rectification; 3) and introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride. The invention utilizes the characteristics of extremely low solubility of the linear primary alcohol in water and the interaction between the linear primary alcohol and HF, and the extraction phase and the raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental protection, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.

Description

Process and apparatus for producing anhydrous hydrogen fluoride
Technical Field
The invention belongs to the technical field of HF separation and recycling, and particularly relates to a process and a device for producing anhydrous hydrogen fluoride.
Background
With the development of the production process in the electronics industry and the fluorine chemical industry, the demand for Anhydrous Hydrogen Fluoride (AHF) is increasing. The existing method for producing AHF by fluorite method has great environmental pollution and is an unsustainable process. Thus, how to derive H from the ubiquitous presence of industrial processes2The production of AHF in O-HF azeotropes (or mixtures) is a current focus. The following methods are reported in the literature: concentrated sulfuric acid extractive distillation, pressure swing distillation, n-hexane stripping, electrodialysis, etc. The concentrated sulfuric acid extractive distillation method has simple process, but has high corrosivity in long-term operation and high requirements on equipment materials; the principle of pressure swing distillation is based on the effect of pressure changes on the azeotropic point of the system, but due to H2The O-HF system has low sensitivity to pressure change and can be realized only by needing larger pressure difference, so the operation cost is obviously increased; the n-hexane stripping method requires a large amount of n-hexane to be recycled, and the operation cost is too high; the electrodialysis method is simple to operate, but the quality standard of AHF is difficult to achieve at one time, and for H2The treatment efficiency of the O-HF azeotrope is low.
Several of the above-mentioned derivatives H2The process method for producing AHF in O-HF azeotrope has the defects of high operation cost, high operation difficulty and the like, and is not widely applied in the industrial production process.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process and a device for producing anhydrous hydrogen fluoride aiming at the defects in the prior artThe extractant is easy to react with HF and H in the extraction and rectification processes2And O is separated, so that the Anhydrous Hydrogen Fluoride (AHF) production process with simple flow, convenient operation and low operation cost is formed.
The technical scheme adopted for solving the technical problem of the invention is to provide a process for producing anhydrous hydrogen fluoride, which comprises the following steps:
1) extracting agent straight-chain primary alcohol CnH2n+2OH、H2Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
2) introducing the extract phase into a first-stage rectifying tower for rectification, and obtaining a first-stage tower top distillate at the tower top of the first-stage rectifying tower, wherein the first-stage tower top distillate comprises hydrogen fluoride and water, and obtaining a first-stage tower bottom at the tower bottom of the first-stage rectifying tower, wherein the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH; this step is from H2Separating the extracting agent in an O-HF-extracting agent ternary system.
3) Introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H2The O-HF azeotrope. This step separates hydrogen fluoride and water.
The extraction rate of HF in the extraction phase at the top of the continuous extraction tower in the step 1) is more than or equal to 99.5 percent. The content of HF in raffinate phase at the bottom of the continuous extraction tower is less than or equal to 0.2 wt%, and the content of straight-chain primary alcohol is less than or equal to 0.05 wt%, and the raffinate phase can be directly used as wastewater for treatment.
And 2) removing the linear primary alcohol of the extractant in the first-stage rectifying tower in the step 2) so as to recycle the extractant.
The second stage rectifying tower in the step 3) is mainly used for treating H2Separating O and HF, and producing industrial AHF product at the tower top.
Preferably, the linear primary alcohols CnH2n+2OH is primary alcohol n-octanol, and n is 8.
Preferably, the linear primary alcohols CnH2n+2OH is n-nonanol or n-decanol.
Preferably, the temperature in the continuous extraction tower in the step 1) is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Preferably, the following step m) is further included after the step 2): and introducing the first-stage tower bottom into a continuous extraction tower for recycling.
In the step 2), the first-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14-17, the position of a feed plate is 7-8, and the reflux ratio is 1.5-2.0.
In the step 3), the second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14-16, the position of a feed plate is 5-6, and the reflux ratio is 1.8-2.1.
Preferably, the following step n) is further included after the step 3): and (4) introducing the secondary tower bottom into a continuous extraction tower for retreatment.
Preferably, the extractant and H in the step 1)2The O-HF azeotropes are contacted countercurrently in a continuous extraction column.
The invention also provides a device for producing anhydrous hydrogen fluoride, which comprises:
a continuous extraction tower for introducing linear primary alcohol C of an extractantnH2n+2OH、H2O-HF azeotrope, extraction of H by extractant2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
the first-stage rectifying tower is connected with the continuous extraction tower, the extract phase enters the first-stage rectifying tower for rectification, a first-stage tower top distillate is obtained at the tower top of the first-stage rectifying tower, the first-stage tower top distillate comprises hydrogen fluoride and water, a first-stage tower bottom is obtained at the tower bottom of the first-stage rectifying tower, and the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH；
A second stage rectifying tower connected with the outlet of the first stage rectifying tower, and the distillate of the first stage rectifying tower is introduced intoRectifying in a second-stage rectifying tower to obtain second-stage overhead distillate at the tower top of the second-stage rectifying tower, wherein the second-stage overhead distillate comprises anhydrous hydrogen fluoride, and obtaining second-stage bottoms at the tower bottom of the second-stage rectifying tower, wherein the second-stage bottoms comprise H2The O-HF azeotrope.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: the inlet of the first heat exchanger is connected with the outlet of the top of the continuous extraction tower, the outlet of the first heat exchanger is connected with the inlet of the first-stage rectifying tower, and the first heat exchanger is used for heating the extraction phase discharged from the top of the continuous extraction tower.
Preferably, in the device for producing anhydrous hydrogen fluoride, the outlet of the bottom of the first-stage rectifying tower is connected with the inlet of the continuous extraction tower.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and the inlet of the second heat exchanger is connected with the outlet at the bottom of the first-stage rectifying tower, the outlet of the second heat exchanger is connected with the inlet of the continuous extraction tower, and the second heat exchanger is used for cooling the first-stage tower bottom discharged from the bottom of the first-stage rectifying tower.
Preferably, in the device for producing anhydrous hydrogen fluoride, the outlet of the second-stage rectifying tower is connected with the inlet of the continuous extraction tower.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the third heat exchanger is connected with an outlet at the bottom of the second-stage rectifying tower, an outlet of the third heat exchanger is connected with an inlet of the continuous extraction tower, and the third heat exchanger is used for cooling a second-stage tower bottom discharged from the bottom of the second-stage rectifying tower.
The invention provides a process for producing Anhydrous Hydrogen Fluoride (AHF), which is characterized in that primary alcohol C based on linear chain is introducednH2n+2OH (n is more than or equal to 8 and less than or equal to 10, and n is an integer) is used as an extracting agent, and H is extracted by continuous extraction2HF in the O-HF azeotrope is transferred to the extraction phase and the extractant is removed in the rectification process to obtain AHF meeting the requirement of industrial product. With the existing various slave H2The process for producing AHF in O-HF azeotropes is different,linear Primary alcohols C used in the inventionnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, and n is an integer) to H2The extraction of the O-HF azeotrope has the following characteristics: (1) compared with sulfuric acid as extractant, linear primary alcohol CnH2n+2OH has no corrosiveness, low requirement on equipment materials, low toxicity and environmental friendliness; n-octanol has a very low hydroxyl activity compared to alcohols based on cycloalkanes or arenes, and does not react with HF during the whole process. (2) Compared with extracting agents such as sulfuric acid, benzyl alcohol and the like, the linear primary alcohol CnH2n+2The OH solubility in water is extremely low, and the n-octanol solubility at 20 ℃ is only 0.05% (5g/100 gH)2O) to facilitate reaction with HF and H during extraction and rectification2And O is separated, so that the AHF production process with simple flow, convenient operation and low running cost is formed.
The innovation of the invention is that: using straight-chain primary alcohols CnH2n+2The characteristic that OH (n is more than or equal to 8 and less than or equal to 10 and n is an integer) has extremely low solubility in water and the characteristic that OH interacts with HF, the extraction and rectification are utilized to extract H2A process for producing AHF from an O-HF azeotrope. Due to the linear primary alcohols CnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, and n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental friendliness, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Drawings
FIG. 1 is a schematic configuration diagram of an apparatus for producing anhydrous hydrogen fluoride according to example 2 of the present invention.
In the figure: 1-a continuous extraction column; 2-a first stage rectification column; 3-a second-stage rectifying tower; 4-a first heat exchanger; 5-a second heat exchanger; 6-third heat exchanger.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Reference will now be made in detail to embodiments of the present patent, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present patent and are not to be construed as limiting the present patent.
Example 1
This example provides a process for producing anhydrous hydrogen fluoride, comprising the steps of:
1) extracting agent straight-chain primary alcohol CnH2n+2OH、H2Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
2) introducing the extract phase into a first-stage rectifying tower for rectification, and obtaining a first-stage tower top distillate at the tower top of the first-stage rectifying tower, wherein the first-stage tower top distillate comprises hydrogen fluoride and water, and obtaining a first-stage tower bottom at the tower bottom of the first-stage rectifying tower, wherein the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH; this step is from H2Separating the extracting agent in an O-HF-extracting agent ternary system.
3) Introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H2The O-HF azeotrope. This step separates hydrogen fluoride and water.
The extraction rate of HF in the extraction phase at the top of the continuous extraction tower in the step 1) is more than or equal to 99.5 percent. The content of HF in raffinate phase at the bottom of the continuous extraction tower is less than or equal to 0.2 wt%, and the content of straight-chain primary alcohol is less than or equal to 0.05 wt%, and the raffinate phase can be directly used as wastewater for treatment.
And 2) removing the linear primary alcohol of the extractant in the first-stage rectifying tower in the step 2) so as to recycle the extractant.
The second stage rectifying tower in the step 3) is mainly used for treating H2Separating O and HF, and producing industrial AHF product at the tower top.
The present embodiment also provides an apparatus for producing anhydrous hydrogen fluoride, which is used in the above method, and includes:
a continuous extraction tower for introducing linear primary alcohol C of an extractantnH2n+2OH、H2O-HF azeotrope, extraction of H by extractant2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
the first-stage rectifying tower is connected with the continuous extraction tower, the extract phase enters the first-stage rectifying tower for rectification, a first-stage tower top distillate is obtained at the tower top of the first-stage rectifying tower, the first-stage tower top distillate comprises hydrogen fluoride and water, a first-stage tower bottom is obtained at the tower bottom of the first-stage rectifying tower, and the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH；
A second-stage rectifying tower connected with the tower top outlet of the first-stage rectifying tower, wherein the first-stage tower top distillate is introduced into the second-stage rectifying tower for rectification, and a second-stage tower top distillate is obtained at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H2The O-HF azeotrope.
The process for producing anhydrous hydrogen fluoride in this example utilizes a linear primary alcohol CnH2n+2The characteristic that OH (n is more than or equal to 8 and less than or equal to 10 and n is an integer) has extremely low solubility in water and the characteristic that OH interacts with HF, the extraction and rectification are utilized to extract H2A process for producing AHF from an O-HF azeotrope. Due to the linear primary alcohols CnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, and n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental friendliness, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Example 2
As shown in fig. 1, the present embodiment provides an apparatus for producing anhydrous hydrogen fluoride, comprising:
a continuous extraction tower 1, and an S1 stream H is introduced into the top inlet of the continuous extraction tower 12An O-HF azeotrope is introduced into a linear primary alcohol C of an S2 stream extractant through a bottom inlet of the continuous extraction tower 1nH2n+2OH, extracting H by an extractant2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an S3 stream raffinate phase at the bottom outlet of the continuous extraction tower 1 and an S4 stream extract phase at the top outlet of the continuous extraction tower 1, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
the first-stage rectifying tower 2 is connected with the continuous extraction tower 1, an S4 stream extract phase enters the first-stage rectifying tower 2 for rectification, an S5 stream first-stage tower top distillate is obtained at the tower top outlet of the first-stage rectifying tower 2, the first-stage tower top distillate comprises hydrogen fluoride and water, an S6 stream first-stage tower bottom is obtained at the tower bottom outlet of the first-stage rectifying tower 2, and the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH；
The second-stage rectifying tower 3 is connected with the tower top outlet of the first-stage rectifying tower 2, the S5 stream first-stage tower top distillate is introduced into the second-stage rectifying tower 3 for rectification, an S7 stream second-stage tower top distillate is obtained at the tower top outlet of the second-stage rectifying tower 3, the second-stage tower top distillate comprises anhydrous hydrogen fluoride, an S8 stream second-stage tower bottom is obtained at the tower bottom outlet of the second-stage rectifying tower 3, and the second-stage tower bottom comprises H8 stream second-stage tower bottom2The O-HF azeotrope.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: an inlet of the first heat exchanger 4 is connected with an outlet at the top of the continuous extraction tower 1, an outlet of the first heat exchanger 4 is connected with an inlet of the first-stage rectifying tower 2, and the first heat exchanger 4 is used for heating an extraction phase discharged from the top of the continuous extraction tower 1.
Preferably, in the device for producing anhydrous hydrogen fluoride, the bottom outlet of the first-stage rectifying tower 2 is connected with the inlet of the continuous extraction tower 1.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the second heat exchanger 5 is connected with an outlet at the bottom of the first-stage rectifying tower 2, an outlet of the second heat exchanger 5 is connected with an inlet of the continuous extraction tower 1, and the second heat exchanger 5 is used for cooling a first-stage tower bottom discharged from the bottom of the first-stage rectifying tower 2.
Preferably, in the apparatus for producing anhydrous hydrogen fluoride, the outlet of the second-stage rectifying column 3 is connected to the inlet of the continuous extraction column 1.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the third heat exchanger 6 is connected with an outlet at the bottom of the second-stage rectifying tower 3, an outlet of the third heat exchanger 6 is connected with an inlet of the continuous extraction tower 1, and the third heat exchanger 6 is used for cooling a second-stage tower bottom discharged from the bottom of the second-stage rectifying tower 3.
The embodiment provides a process for producing anhydrous hydrogen fluoride by using the device, which comprises the following steps:
1) extracting the S2 stream with linear primary alcohol C under normal temperature and pressure conditionsnH2n+2OH, S1 stream H2Introducing the O-HF azeotrope into a continuous extraction tower 1, and extracting with linear primary alcohol CnH2n+2OH enters from the top of the continuous extraction tower 1, H2The O-HF azeotrope enters from the bottom of a continuous extraction tower 1, wherein n is 8, and the extracting agent is n-octanol.
Material stream S1 is H2O-HF azeotrope with a treatment capacity of 1100kg/hr, HF content of 37.2 wt%, temperature of 20 ℃ and pressure of 1.1 bar.
Stream S2 was an extractant, n-octanol, at a flow rate of 1500kg/hr, a temperature of 20 ℃ and a pressure of 1.1 bar.
Extraction of H by means of an extractant2Hydrogen fluoride in the O-HF azeotrope, streams S1 and S2 are in countercurrent contact in the continuous extraction tower 1, an extract phase (an alcohol phase) is obtained at the top of the continuous extraction tower 1, and a raffinate phase (an aqueous phase) is obtained at the bottom of the continuous extraction tower 1. The continuous extraction tower 1 adopts a sieve plate tower, the number of tower plates is 22, and the operation is carried out under the conditions of normal temperature and normal pressure. In stream S4 extracted from the top of the continuous extraction tower 1, n-octanol is 1499.7kg/hr, HF is 407.5kg/hr, and H is2O was 103.5 kg/hr. H in stream S3 taken from the bottom of the continuous extraction column 12O587.3 kg/hr, HF 1.751kg/hr, and n-octanol 0.257 kg/hr.
The extraction rate of HF in the extraction phase at the top of the continuous extraction column 1 is not less than 99.5%, wherein the content of n-octanol is about 74.6 wt%, the content of HF is about 20.3 wt%, and H is2The O content was about 5.1 wt%. Water content in raffinate phase at the bottom of continuous extraction column 1>99.7 wt%, HF content less than or equal to 0.2 wt%, and n-octanol content less than or equal to 0.05 wt%, and can be directly discharged to downstream waste water treatment section as waste water for treatment.
2) And the stream S4 is heated to a bubble point, specifically 47 ℃, through a first heat exchanger 4 and enters a first-stage rectifying tower 2 to remove n-octanol. Obtaining a first-stage overhead distillate at the top of the first-stage rectifying tower 2, wherein the first-stage overhead distillate comprises a large amount of hydrogen fluoride and a small amount of water, and obtaining a first-stage bottom at the bottom of the first-stage rectifying tower 2, wherein the first-stage bottom comprises linear primary alcohol CnH2n+2OH, and a small amount of hydrogen fluoride and water; this step is from H2Separating the extracting agent in an O-HF-extracting agent ternary system. The first-stage rectifying tower 2 removes the straight-chain primary alcohol of the extracting agent so as to recycle the extracting agent.
Specifically, the first-stage rectifying tower 2 adopts a packed tower, the number of effective tower plates is 16, the position of a feed plate is 7, the reflux ratio is 1.8, the top heat load of the first-stage rectifying tower 2 is-321.9 kW, and the bottom heat load of the first-stage rectifying tower 2 is 424.4 kW. A stream S5 is obtained from the top of the first stage rectifying tower 2 at 26.3 deg.C and 1.001bar pressure, wherein HF is 400.9kg/hr and H is2O is 78.4kg/hr, and n-octanol is 0.644 kg/hr. Stream S6 is obtained from the bottom of the first stage rectifying tower 2 at 130.0 deg.C under 1.010bar pressure, wherein n-octanol is 1499.1kg/hr, HF is 6.501kg/hr, and H is2O was 25.09 kg/hr.
3) And cooling the stream S6 to 20 ℃ through a second heat exchanger 5, and mixing the stream S2 to realize the recycling of the extractant. And cooling the primary tower bottom by a second heat exchanger 5, and then circulating the primary tower bottom to the continuous extraction tower 1 for recycling.
4) Introducing the first-stage tower top distillate into a second-stage rectifying tower 3 for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower 3, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower 3,wherein the secondary bottoms comprises H2The O-HF azeotrope. The step of separating hydrogen fluoride and water, and the second-stage rectifying tower 3 is mainly used for treating H2Separating O and HF, and producing industrial AHF product at the tower top.
Specifically, stream S5 enters second stage rectifier 3 at bubble point. The second-stage rectifying tower 3 adopts a packed tower, the number of effective tower plates is 15, the position of a feed plate is 5, the reflux ratio is 2, the heat load at the top of the tower is 110.9kW, and the heat load at the bottom of the tower is 116.1 kW. The stream S7 extracted from the top of the second stage rectifying tower 3 is AHF product, the temperature is 19.3 ℃, the pressure is 1.001bar, wherein the HF is 360.0kg/hr, and H is2The content of O and n-octanol is less than 0.288 kg/hr. Stream S8 is obtained from the bottom of the second stage rectifying tower 3 at 112.2 deg.C under 1.010bar pressure, wherein n-octanol is 0.644kg/hr, HF is 40.94kg/hr, and H is2O was 78.42 kg/hr.
5) Stream S8 was cooled to 20 ℃ by third heat exchanger 6, mixed with stream S1 and fed to the feed inlet of continuous extractor 1.
The process for producing anhydrous hydrogen fluoride in this example utilizes a linear primary alcohol CnH2n+2The characteristic that OH (n is more than or equal to 8 and less than or equal to 10 and n is an integer) has extremely low solubility in water and the characteristic that OH interacts with HF, the extraction and rectification are utilized to extract H2A process for producing AHF from an O-HF azeotrope. Due to the linear primary alcohols CnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, and n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental friendliness, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Example 3
This example provides a process using the apparatus for producing anhydrous hydrogen fluoride of example 2, which differs from the process of example 2 in that:
the temperature in the continuous extraction tower is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Extractant straight-chain primary alcohol CnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, n is an integer), specifically, n is 9, and the extracting agent is straight-chain n-nonanol.
The first stage of rectifying tower adopts a packed tower, the number of effective tower plates is 14, the position of a feed plate is 8, and the reflux ratio is 1.5.
The second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14, the position of a feed plate is 6, and the reflux ratio is 1.8.
Example 4
This example provides a process using the apparatus for producing anhydrous hydrogen fluoride of example 2, which differs from the process of example 2 in that:
the temperature in the continuous extraction tower is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Extractant straight-chain primary alcohol CnH2n+2OH (n is more than or equal to 8 and less than or equal to 10, n is an integer), specifically, n is 10, and the extracting agent is straight-chain n-decanol.
The first stage of rectifying tower adopts a packed tower, 17 effective tower plates are arranged, the position of a feed plate is 7, and the reflux ratio is 2.0.
The second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 16, the position of a feed plate is 5, and the reflux ratio is 2.1.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.

Claims (13)

1. A process for producing anhydrous hydrogen fluoride comprising the steps of:
1) extracting agent straight-chain primary alcohol CnH2n+2OH、H2Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
2) introducing the extract phase into a first-stage rectifying tower for rectification to obtain a first-stage tower top distillation at the tower top of the first-stage rectifying towerDischarging, wherein the primary tower top distillate comprises hydrogen fluoride and water, and obtaining primary tower bottom at the tower bottom of the first-stage rectifying tower, wherein the primary tower bottom comprises linear primary alcohol CnH2n+2OH；
3) Introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H2The O-HF azeotrope.
2. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the linear primary alcohol C isnH2n+2OH is primary alcohol n-octanol, and n is 8.
3. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the temperature in the continuous extraction column in the step 1) is 5 to 35 ℃ and the pressure is 0.81325 to 1.21325 bar.
4. The process for producing anhydrous hydrogen fluoride according to claim 1, further comprising the following step m) after the step 2): and introducing the first-stage tower bottom into a continuous extraction tower for recycling.
5. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the first-stage rectifying tower in the step 2) is a packed tower, the number of effective plates is 14 to 17, the position of the feed plate is 7 to 8, and the reflux ratio is 1.5 to 2.0.
6. The process for producing anhydrous hydrogen fluoride according to claim 1, further characterized in that the second-stage rectification column in the step 3) is a packed column, the effective number of the trays is 14-16, the position of the feed plate is 5-6, and the reflux ratio is 1.8-2.1.
7. The process for producing anhydrous hydrogen fluoride according to claim 1, further comprising the following step n) after the step 3): and (4) introducing the secondary tower bottom into a continuous extraction tower for retreatment.
8. An apparatus for producing anhydrous hydrogen fluoride, which is used in the process according to any one of claims 1 to 7, comprising:
a continuous extraction tower for introducing linear primary alcohol C of an extractantnH2n+2OH、H2O-HF azeotrope, extraction of H by extractant2Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10, and is an integer;
the first-stage rectifying tower is connected with the continuous extraction tower, the extract phase enters the first-stage rectifying tower for rectification, a first-stage tower top distillate is obtained at the tower top of the first-stage rectifying tower, the first-stage tower top distillate comprises hydrogen fluoride and water, a first-stage tower bottom is obtained at the tower bottom of the first-stage rectifying tower, and the first-stage tower bottom comprises linear primary alcohol CnH2n+2OH；
A second-stage rectifying tower connected with the tower top outlet of the first-stage rectifying tower, wherein the first-stage tower top distillate is introduced into the second-stage rectifying tower for rectification, and a second-stage tower top distillate is obtained at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H2The O-HF azeotrope.
9. The apparatus for producing anhydrous hydrogen fluoride according to claim 8, further comprising: the inlet of the first heat exchanger is connected with the outlet of the top of the continuous extraction tower, the outlet of the first heat exchanger is connected with the inlet of the first-stage rectifying tower, and the first heat exchanger is used for heating the extraction phase discharged from the top of the continuous extraction tower.
10. The apparatus for producing anhydrous hydrogen fluoride according to claim 8, wherein the bottom outlet of the first-stage rectifying column is connected to the inlet of the continuous extraction column.
11. The apparatus for producing anhydrous hydrogen fluoride according to claim 10, further comprising: and the inlet of the second heat exchanger is connected with the outlet at the bottom of the first-stage rectifying tower, the outlet of the second heat exchanger is connected with the inlet of the continuous extraction tower, and the second heat exchanger is used for cooling the first-stage tower bottom discharged from the bottom of the first-stage rectifying tower.
12. The apparatus for producing anhydrous hydrogen fluoride according to claim 8, wherein the bottom outlet of the second-stage rectifying column is connected to the inlet of the continuous extraction column.
13. The apparatus for producing anhydrous hydrogen fluoride according to claim 12, further comprising: and an inlet of the third heat exchanger is connected with an outlet at the bottom of the second-stage rectifying tower, an outlet of the third heat exchanger is connected with an inlet of the continuous extraction tower, and the third heat exchanger is used for cooling a second-stage tower bottom discharged from the bottom of the second-stage rectifying tower.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735063A (en) * 2021-09-26 2021-12-03 苏州金宏气体股份有限公司 Purification device and purification process for 9N electronic grade HF

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1054745A (en) * 1963-02-13
US3947558A (en) * 1973-08-16 1976-03-30 Dow Chemical (Nederland) B.V. Method of recovering HF from mixtures containing C1 -C3 halocarbon compounds
WO2012011609A1 (en) * 2010-07-23 2012-01-26 Daikin Industries, Ltd. Purification method of 2,3,3,3-tetrafluoropropene
CN105947984A (en) * 2016-05-20 2016-09-21 同济大学 Production process for recycling and producing anhydrous hydrogen fluoride from high-concentration wastewater containing fluoride
JP2016179977A (en) * 2011-07-08 2016-10-13 アルケマ フランス Method for separating and recovering 2,3,3,3-tetrafluoropropene and hydrofluoric acid
CN106977034A (en) * 2017-03-16 2017-07-25 中国核电工程有限公司 A kind of method that hydrogen fluoride is reclaimed from high-concentration fluorine-containing waste water
RU2016140317A (en) * 2016-10-12 2018-04-12 Акционерное общество "Ангарский электролизный химический комбинат" METHOD FOR SEPARATING NIOBIUM AND TANTAL

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1054745A (en) * 1963-02-13
US3271273A (en) * 1963-02-13 1966-09-06 Halcon International Inc Distillation process for recovering anhydrous hydrogen fluoride
US3947558A (en) * 1973-08-16 1976-03-30 Dow Chemical (Nederland) B.V. Method of recovering HF from mixtures containing C1 -C3 halocarbon compounds
WO2012011609A1 (en) * 2010-07-23 2012-01-26 Daikin Industries, Ltd. Purification method of 2,3,3,3-tetrafluoropropene
JP2016179977A (en) * 2011-07-08 2016-10-13 アルケマ フランス Method for separating and recovering 2,3,3,3-tetrafluoropropene and hydrofluoric acid
CN105947984A (en) * 2016-05-20 2016-09-21 同济大学 Production process for recycling and producing anhydrous hydrogen fluoride from high-concentration wastewater containing fluoride
RU2016140317A (en) * 2016-10-12 2018-04-12 Акционерное общество "Ангарский электролизный химический комбинат" METHOD FOR SEPARATING NIOBIUM AND TANTAL
CN106977034A (en) * 2017-03-16 2017-07-25 中国核电工程有限公司 A kind of method that hydrogen fluoride is reclaimed from high-concentration fluorine-containing waste water

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
TOREK, K ET AL: "REDUCED PRESSURE ETCHING OF THERMAL OXIDES IN ANHYDROUS HF/ALCOHOLIC GAS-MIXTURES", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY 》 *
蔡晓强 等: "可忽略损耗液相微萃取法同时测定辛醇-水分配系数和电离常数", 《分析试验室》 *
轻工学院<有机化学>编写组 编: "《有机化学》", 30 June 1988, 北京师范学院出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735063A (en) * 2021-09-26 2021-12-03 苏州金宏气体股份有限公司 Purification device and purification process for 9N electronic grade HF

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